Anisotropic nanoparticles and anisotropic nanostructures and pixels, displays and inks using them

ABSTRACT

A pixel that includes a liquid crystal material and one or more of an anisotropic nanoparticle and an anisotropic nanostructure is provided. Displays including the pixel are also disclosed. An ink which includes a liquid crystal material and one or more of an anisotropic nanoparticle and an anisotropic nanostructure is also provided.

PRIORITY APPLICATIONS

This application claims the benefit under 35 U.S.C. § 119(e) to U.S.Provisional Application No. 60/557,955 filed Mar. 31, 2004 and entitled“ALIGNMENT OF ANISOTROPIC NANOSTRUCTURES FOR DISPLAY APPLICATIONS,” andto U.S. Provisional Application No. 60/591,486 filed Jul. 27, 2004 andentitled “ALIGNMENT OF ANISOTROPIC NANOSTRUCTURES FOR DISPLAYAPPLICATIONS,” the entire disclosures of each of which are herebyincorporated herein by reference for all purposes.

FIELD OF THE TECHNOLOGY

Certain examples disclosed herein relate to the use of anisotropicnanoparticles and anisotropic nanostructures in pixels, displays andinks. More particularly, certain examples disclosed herein relate to theuse of liquid crystal materials and metallic and semiconductingnanostructures with asymmetric shapes to provide optically improvedpixel, displays and/or inks.

BACKGROUND

Localized surface plasmons have been observed since the Romans who usedgold and silver nanoparticles to create colored glass objects such asthe Lycurgus Cup (4^(th) Century AD). A gold sol in the British museum,created by Michael Faraday in 1857, is still exhibiting its red colordue to the plasmon resonance at ˜530 nm. In more recent times, localizedplasmons have been observed on rough surfaces and in engineerednanostructures and have led to the observation and exploitation ofSurface Enhanced Raman Scattering (SERS) and new tunable plasmonstructures with potential applications in biology and medicine.

SUMMARY

In accordance with a first aspect, a pixel is provided. In certainexamples, the pixel comprises a liquid crystal material and ananisotropic nanoparticle. In other examples, the pixel comprises aliquid crystal material and an anisotropic nanostructure. In certainexamples, the pixel may include a liquid crystal material, ananisotropic nanoparticle and an anisotropic nanostructure. In someexamples, the pixel may include a liquid crystal material and aplurality of anisotropic nanoparticles and/or a plurality of anisotropicnanostructures, each of which may or may not be encapsulated.

In accordance with an additional aspect, a liquid crystal display isdisclosed. In certain examples, the liquid crystal display comprises apixel that includes a liquid crystal material and an anisotropicnanoparticle. In other examples, the liquid crystal display comprises apixel that includes a liquid crystal material and an anisotropicnanostructure. In certain examples, the display comprises a pixel thatincludes a liquid crystal material, an anisotropic nanoparticle and ananisotropic nanostructure. In some examples, the liquid crystal displaycomprises a plurality of pixels wherein each of the pixels includes aliquid crystal material and one or more of an anisotropic nanoparticleor an anisotropic nanostructure.

In accordance with another aspect, an ink comprising a liquid crystalmaterial and one or more of an anisotropic nanoparticle or ananisotropic nanostructure is disclosed. In certain examples, the inkcomprises a liquid crystal material and plurality of anisotropicnanoparticles and/or a plurality of anisotropic nanostructures. In someexamples, the liquid crystal material and the anisotropic nanoparticle,or the plurality of anisotropic nanoparticles, may be encapsulated toform microcapsules. In other examples, the liquid crystal material andthe anisotropic nanostructure, or the plurality of anisotropicnanostructures, may be encapsulated to form microcapsules. In someexamples, the ink may also include a carrier.

In accordance with an additional aspect, a method of doping a liquidcrystal display pixel is disclosed. In certain examples, the methodincludes doping a liquid crystal display pixel with one or more of ananisotropic nanoparticle or an anisotropic nanostructure. The liquidcrystal display pixel typically includes a liquid crystal material towhich nanoparticle dopant or nanostructure dopant is added.

These and other aspects and features are further described in moredetail below, and additional aspects and features that use thetechnology described herein will be readily selected by the person ofordinary skill in the art, given the benefit of this disclosure.

BRIEF DESCRIPTION OF THE FIGURES

Certain examples are described below with reference to the accompanyingfigures in which:

FIG. 1A is a schematic of an anisotropic nanorod and FIG. 1B is aschematic of an anisotropic nanoellipse, each of which may be orientedin response to a stimulus, in accordance with certain examples;

FIG. 2 is a schematic of long chain molecule or carbon nanotubeincluding semiconductor or metal nanoparticles such as those of FIGS. 1Aand 1B, in accordance with certain examples;

FIG. 3 is a schematic of carbon nanotube including associatedfluorescent chromophores, in accordance with certain examples;

FIGS. 4A and 4B are schematic examples of a transmissive or reflectivepixel, in a first state (FIG. 4A) and a second state (FIG. 4B),including anisotropic nanostructures such as those of FIG. 1 or FIG. 2,in accordance with certain examples;

FIGS. 5A and 5B are schematic examples of an emissive pixel, in a firststate (FIG. 5A) and a second state (FIG. 5B), including a plurality ofanisotropic nanostructures such as those in FIG. 3, in accordance withcertain examples;

FIG. 6 is a schematic of a pixel including microencapsulated anisotropicnanostructures, in accordance with certain examples;

FIG. 7 is a schematic of a printable ink including microencapsulatedanisotropic nanostructures in a carrier, in accordance with certainexamples;

FIG. 8 is a schematic of a polymer dispersed liquid crystal (PDLC) pixelwith anisotropic nanostructures, in accordance with certain examples;and

FIG. 9 is a schematic of a graph of degree of orientation versus voltagefor a bistable pixel, in accordance with certain examples.

It will be recognized by the person of ordinary skill in the art, giventhe benefit of this disclosure, that certain features or components inthe figures may have been enlarged or distorted relative to the size ordimensions of other features or components in the figures to provide amore user friendly version of the figures and to facilitate a betterunderstanding of the novel technology described herein.

DETAILED DESCRIPTION

Certain examples of the technology disclosed herein provide significantbenefits over existing pixel and liquid crystal display configurations.For example, the pixels and display provided herein may provide widerviewing angles, may reduce chromatic distortion at different viewingangles, do not suffer from bleaching problems observed with dichroic dyemolecules (See “Handbook of Display Technology” by Joseph A. Castellano,Academic Press (1992), p. 219), and may provide better resolution andblack levels than existing liquid crystal displays. Such improvements inthe pixels and displays are referred to generally in certain instancesherein as a “visual enhancement” or “visual enhancements.” These andother advantages and benefits of the technology disclosed herein, willbe readily recognized by the person of ordinary skill in the art, giventhe benefit of this disclosure.

In accordance with certain examples, particles, such as, for example,metallic particles are known to exhibit plasmon resonances which are afunction of shape, material properties, surrounding material responsesand orientation relative to the polarization of the incident light. Suchparticles are referred to in some instances herein as “nanoparticles.” A“nanostructure,” as used herein and as defined further below, refers toa structure, such as, for example, a carbon nanotube or nanorod, whichmay optionally include one or more nanoparticles. Examples ofnanoparticles and nanostructures are described in more detail herein.These systems have been shown to exhibit shifted and altered responsesto electromagnetic waves when they are in the form of aggregates or havefractal structures. Examples of this are seen in Surface Enhanced RamanScattering (SERS). Gold and silver colloids, for example, have beenshown to undergo strong color changes when they are concentrated due tointeractions between colloid particles. These changes are illustrated,for example, in Michael Quinten: “Optical Effects Associated withAggregates of Clusters”, Journal of Cluster Science, Vol. 10. No. 2,1999. For example, for silver particles, the isolated particle sampleappears yellow due to the surface plasmon, which is peaked at thewavelengths of blue light. The color of the aggregated samples changes,however, into orange, brown, and green as the amount of silver particlesin the aggregate increases. For gold, the red color of the isolatedparticle sample changes for the aggregated sample into violet and blueas the amount of gold particles in the aggregate increases. The role ofinter-particle separation on the color has been demonstrated by Kotov etal. (J. Phys. Chem. (1995) 99, 13065) where multilayers of SiO₂ coatedgold nanoparticles are formed. Particles with thicker shells are redishwhereas particles which have thinner shells and are closer, are blue.

There has been a significant amount of work focused on the synthesis ofmetallic and semiconducting nanostructures with asymmetric shapes. Mostdeveloped is the class of materials called nanorods. Examples of nanorodmodels of the absorptive and scattering response in the long wavelengthlimit are shown by Van Duyne, et al. “Electromagnetic Mechanism ofSurface-enhanced Spectroscopy” from the Handbook of VibrationalSpectroscopy, John Wiley & Sons Ltd, 2002. These structures have beenmade from pure and compound semiconductors as well as metals such asgold, silver and alloys. The methods of synthesis include vapor phaseand solution chemistry. Reference in this regard may be made to N. R.Jana, L. Gearhart and C. J. Murphy, J. Phys. Chem. B 105, 4065, 2001.Structures which have an inner and outer core and possess asymmetry havealso been developed. These include nanorods with sheaths, with the metalinside or outside or the use of two different semiconductors for eachlayer. Another class of materials is referred to as nanotubes, e.g.,carbon nanotubes. These structures may be a single wall or a multiwallstructure and may be formed in a variety of shapes.

In accordance with certain examples, the surfaces of nanoparticles andnanostructures may also be functionalized and chromophores mayassociated, e.g., reversibly or irreversibly. For example, nanotubes maybe capped to create structures such as nanohorns. Carbon nanotubes andother moieties of the structures can be doped with various species,e.g., nanoparticles, including metal atoms and can also be used asscaffolds for the attachment of nanoparticles of noble metals andsemiconductors. An example of this method of creating anisotropicnanometal structures in this regard may be made to “Linear Assemblies ofSilica-Coated Gold Nanoparticles using Carbon Nanotubes as Templates”,by Correa-Duante et al., Adv. Mater. 2004, 16(23), p. 2179. A commonfeature of these structures, including arrays created on scaffolds, hasthe property that its absorption and scattering of light is a functionof its orientation relative to the polarization of light. In metallicsystems, the plasmon resonances are different in the direction of thelong axis and short axis respectively. Varying the aspect ratio canproduce noticeable changes in the color of the solutions of rods even inthe case of random orientation. Reference in this regard may be made to“Controlling the Aspect Ratio of Inorganic Nanorods and Nanowires” by C.J. Murphy, Adv. Mater. 2002, 14(80). In the case of semiconductors andcarbon nanotubes, the absorption is highly anisotropic. In the case ofplasmon resonance, not only is the position of the resonance differentbut the strength of the resonance along an axis and the strength of theresonance orthogonal to the axis are different. For gold nanorods, thelinewidth of the long axis plasmon resonance can be considerablynarrower.

Nanorods and rod like structures may be oriented by electric fields.See, for example, “Alignment of Rod-Shaped Gold Particles by ElectricFields”, Van der Zande et al. J. Phys. Chem. B. 103(5754), 1999.Nanorods and rod like structures may be oriented when embedded withinliquid crystals (which may also be orientable using electric fields).Recent work at the University of Manchester has demonstrated this effectwith carbon nanotubes while similar effects have been observed with CdSenanorods. Reference in this regard may be made to “Aligning andReorienting Carbon Nanotubes with Nematic Liquid Crystals”, by Dierkinget al., Adv. Mater. 2004, 16(11) Pg. 865. The basic effect is from theminimization of the free energy, the entire fluid is minimized by theorientation of the nanostructures, e.g., carbon nanotubes, and theliquid crystals.

It is also been shown that when nanoparticles are brought close enoughto interact, such as a string of spherical particles on carbon nanotubesor attached to DNA, an anisotropic structure may be formed. Reference inthis regard may be made to “Organization of ‘nanocrystal molecules’using DNA” by A. Paul Alivisatos, et al. Nature 382 (609) 1996.

Most of the liquid crystal (LC) displays today suffer from severechromatic distortion when viewed at different angles, e.g., colors areshifted at non-orthogonal or non, near-orthogonal viewing angles.Existing displays also are limited in their brightness as much of thelight is lost in the polarization requirement of some LC systems.Existing displays also have limited viewing angles. These negativeattributes lead to gaps in the price performance matrices for displaysand have limited the applications of LC displays.

In accordance with certain examples, the exact nature and chemicalmakeup of the nanoparticles used in the exemplary pixels, displays andinks disclosed herein may vary depending on the device that uses them.In some examples, the nanoparticles are charged or receptive to beingcharged (e.g., positive, negative, a partial positive charge, a partialnegative charge or a dipole), whereas in other examples, thenanoparticles are uncharged or neutral. In certain examples, ananoparticle comprises a non-conductive material, a conductive materialor a semi-conductive material. In some examples, the nanoparticlecomprises two or more of a non-conductive material, a conductivematerial and a semi-conductive material. In examples where thenanoparticle includes a non-conductive material, the non-conductivematerial may be selected from one or more of titania, zinc oxide, clays,magnesium silicate, glasses or other suitable non-conductive materials.In examples where the nanoparticle includes a conductive material, theconductive material may be selected from metals, or combinations ofmetals, such as, for example, transition metals and alloys of thesemetals. In certain examples, the conductive material includes one ormore of silver, gold, platinum, palladium, ruthenium, rhodium, osmium,iridium and alloys of these metals. In examples where the nanoparticleincludes semi-conductive materials, the semi-conductive material may beselected from one or more of cadmium selenide, cadmium telluride, zincselenide, zinc telluride, cadmium phosphide, cadmium arsenide, galliumselenide, aluminum arsenide and the like. It will be recognized by theperson of ordinary skill in the art, given the benefit of thisdisclosure, that the optical characteristics of a pixel, display or inkmay vary depending on the composition of the nanoparticles and thatnon-conductive nanoparticles, conductive nanoparticles andsemi-conductive nanoparticles may not provide the same optical responsewhen concentrated. In some examples, one or more nanoparticles may bepart of a larger structure such as, for example, a nanostructure. Inother examples, a core shell nanostructure may be used in the pixels,display and inks disclosed herein. Additional examples of nanoparticlesand materials suitable for use in the pixels, displays and inks providedherein may be found, for example, in U.S. Pat. No. 5,882,779 and incommonly owned U.S. patent application Ser. No. ______ (bearing AttorneyDocket No. S2012-700110) and entitled “Plasmon Nanoparticles and Pixels,Displays and Inks Using Them” and filed on Mar. 28, 2005, the entiredisclosure of each of which is hereby incorporated herein by referencefor all purposes.

In accordance with certain examples, the overall shape of thenanoparticles and nanostructures disclosed herein may vary. For example,the nanoparticles, or nanostructures, may be elliptical, spheroid,triangular, rectangular, or may take other suitable geometries commonlyfound in atomic and molecular structures. In some examples, thenanoparticle may include an electrically conductive shell around aninsulating core, or an electrically insulating shell around a conductivecore. For example, an insulating core may be formed from non-conductivematerials such as those described herein. In certain examples, ananoparticle may include an inner medium, which may be, for example, ametal or a dielectric. The nanoparticle may also include an outermedium, which may be, for example, a dielectric or metal that surroundsthe inner medium. The nanoparticle may also include an external medium,which may be a surrounding dielectric medium. In certain examples, thedielectric for any one or more of inner, outer or external media may bea fluid, such as a gas, liquid, supercritical fluid and the like. Insome examples, the dielectric is selected from one or more materialsthat are non-conductive at the frequencies (or wavelengths) of interestor is a material which does not possess a negative real dielectricconstant. Illustrative examples of dielectric materials suitable for usein pixels, displays and inks include, but are not limited to, oxides,such as TiO₂, ZnO, SiO₂, or polymeric materials such as PMMA or styrene.Depending on the material properties, size and shape geometries ofnanoparticles, e.g., core-shell nanoparticles, they can be made toexhibit a specific plasmon resonance. In some examples, nanoparticlesmay also be made of a single medium of material, e.g., a metal. Theperson of ordinary skill in the art, given the benefit of thisdisclosure, will be able to select and/or design suitable nanoparticlesfor use in the illustrative pixels, displays and inks disclosed herein.Exemplary nanoparticles suitable for use in the pixels, displays andinks disclosed herein include, but are not limited to, those describedin Liz-Marzan, L. M. “Nanometals: Formation and Color.” Materials Today,pp. 26-31 (February 2004). Illustrative methods for producingnanoparticles include, but are not limited to, those methods describedin U.S. Pat. No. 5,882,779, the entire disclosure of which is herebyincorporated herein by reference for all purposes.

In accordance with certain examples, the exact size, e.g., diameter, ofthe nanoparticles used in the exemplary pixels, displays and inksdisclosed herein may vary, but the particle size is typically muchsmaller than the wavelength of transmitted, reflected or emitted light.In certain examples, the smallest dimension of the diameter of ananoparticle filled microcapsule, or a nanostructure filledmicrocapsule, is less than about 500 nm, more particularly less thanabout 200 nm or 100 nm, e.g., about 50 nm in diameter, 25 nm in diameteror less. Similarly, the exact form or topology of any higher orderedstructures that may form from the nanoparticles, or the nanostructures,may vary and illustrative forms include, but are not limited to, fractalstructures, linear forms, cross-shaped forms, T-shaped forms,trapezoid-shaped forms, U-shaped forms, gamma shaped forms,corner-shaped forms or other suitable forms that the aggregate mayadopt. The concentration of the nanoparticles (or nanostructures) mayvary depending on the intended use, e.g., pixel, ink, etc., and theparticular chemical makeup of the nanoparticles.

In accordance with certain examples, a suitable nanoparticle (ornanostructure) concentration includes, but is not limited, to thoseconcentrations that are effective to improve the optical properties ofthe pixel, e.g., to provide visual enhancement by one or more ofreducing chromatic distortion, widening the viewing angle, providingbetter black levels, providing better contrast and/or resolution and thelike. In certain examples, pixels comprising an anisotropic nanoparticleor an anisotropic nanostructure, or both, may be configured to reducechromatic distortion as a function of viewing angle when non-orthogonal,e.g., reduce chromatic distortion by at least 10% as compared to theamount of chromatic distortion present in a pixel comprising a liquidcrystal material but no anisotropic nanoparticle or an anisotropicnanostructure. For example, as a viewer moves from a viewing angle thatis orthogonal to the display screen to a viewing angle that is about15-20 degrees from orthogonal, chromatic distortion in the pixelprovided herein may be reduced by at least about 10% as compared to theamount of chromatic distortion present in a pixel including a liquidcrystal material but no anisotropic nanoparticle or an anisotropicnanostructure. Additional suitable sizes, forms and concentrations thatprovide visual enhancement will be readily selected by the person ofordinary skill in the art, given the benefit of this disclosure.

In accordance with certain examples, nanoparticles, or nanostructures,suitable for use in the pixels, displays and inks disclosed herein mayalso include modified surfaces. For example, the surface of ananoparticle, or one or more surfaces of a nanostructure, may bemodified to be magnetic, modified to have charged and/or unchargedgroups, modified to render the nanoparticle asymmetric or anisotropic,or may be modified in other suitable manners using suitable chemicalreagents, such as those commonly used to accomplish chemical surfacemodification. The use of anisotropic nanoparticles may lead topolarization sensitive concentration color effects which may be usefulfor pixels, displays and inks.

In accordance with certain examples, the exact nature and composition ofa liquid crystal (LC) in a pixel, such as a liquid crystal display pixelsuitable for use in a liquid crystal display, may vary. The pixel mayinclude only a single type of LC, multiple different types of LCs, etc.In certain examples, the LC is one or more of a nematic liquid crystal,a twisted nematic liquid crystal, a ferroelectric liquid crystal, asurface stabilized ferroelectric liquid crystal, and an E7 liquidcrystal. The liquid crystal may be free in a medium or may beintercalated or dispersed in a host matrix, such as a polymer hostmatrix, e.g., a polymer dispersed liquid crystal (PDLC) host asdescribed herein. The person of ordinary skill in the art, given thebenefit of this disclosure, will be able to select suitable LCs and LChost materials for use in the pixels, displays and inks disclosedherein.

In accordance with certain examples, a dramatic change in light emissionmay occur if an orientation change is achieved in an anisotropicnanoparticle, or in an anisotropic nanostructure, where the absorptionand emission drastically change to suppress or enhance transmission,reflection or emission depending on an initial and a final orientationrelative to the incident polarization. For example and referring toFIGS. 1A and 1B, two schematic examples of an anisotropic nanostructure10 and 15 are shown. In the configuration shown in FIG. 1A, thenanostructure 10 is in the form of a rod, e.g., a nanorod or a nanotube,where a radial dimension R₁ is not equal to an axial dimension A₁. Inthe configuration shown in FIG. 1B, a nanoellipse 15 is shown.Nanoparticles or nanostructures, e.g., nanorods, nanotubes,nanoellipses, core shell structures and other high aspect ratiostructures, may be reversibly oriented such that their long axis isparallel or orthogonal to a plane of excitation polarization. The personof ordinary skill in the art, given the benefit of this disclosure, willbe able to design suitable pixels, displays and inks comprisingnanoparticles and nanostructures that are capable of orienting parallelor orthogonal to the plane of excitation polarization.

In accordance with certain examples, elongated nanoparticles andnanostructures, e.g., nanotubes, nanorods, nanoellipses, core shellstructures and other high aspect ratio structures, may be formed, forexample, by linking semiconductor or metal nanoparticle spheres 21 (oranisotropic nanostructure 10 or 15) along a wall or side 22 of longchain molecule or carbon nanotube, as depicted schematically in FIG. 2,to form nanostructure 20. It will be recognized by the person ofordinary skill in the art, given the benefit of this disclosure, thatthe individual components of an anisotropic nanostructure need not beanisotropic (though they may be) as long as the overall nanostructure isanisotropic.

In certain examples, anisotropic nanostructures may be formed by linkingone or more luminescent chromophores, e.g., chromophores whichfluoresce, phosphoresce or scatter light after being excited, to ananoparticle or other suitable structure, such as a carbon nanotube. Forexample and referring to FIG. 3, a carbon nanotube 32 includes attachedfluorescent chromophores, such as fluorescent chromophore 34, to form ananisotropic nanostructure 30. The fluorescent chromophore 34 may becovalently linked with carbon nanotube 32, may irreversibly orreversibly associate with the carbon nanotube 32 through one or moreionic or dipole interactions or may interact with carbon nanotube 32using other suitable interactions. In examples where the fluorescentchromophore reversibly associates with the carbon nanotube, thedissociation constant is may be 10⁻⁹ moles/L or less to provide tightbinding. Depending on the initial and final orientations (relative toincident polarization) of the nanostructure 30, the nanostructure 30 maybe used to suppress or enhance light emission, transmission andreflection. In addition, other suitable elements, e.g., polarizers, maybe employed to enhance contrast.

In accordance with certain examples, the anisotropic nanoparticlesand/or anisotropic nanostructures disclosed herein may orient inresponse to a stimulus, such as an electric field, magnetic field,acoustic wave, pressure or temperature gradients, hydrodynamic forces,thermophoretic forces, electrophoretic forces and the like. In someexamples, the orientation may be created by direct action of an electricfield or a magnetic field on the anisotropic nanoparticles which may ormay not have dipoles or charges. In other examples, the orientation maybe accomplished by hydrodynamic forces created by an orientable fluidsuch a liquid crystal (LC) material or a free energy minimizationleading to a naturally oriented phase at high rod density. Nanorods ornanotubes in LC materials, which are randomly oriented, may themselvesbe randomly oriented. If the LC director field is oriented, the nanorodsor nanotubes may also orient to minimize free energy. Such effects havebeen realized with LCs and long chain dyes. In certain examples, theanisotropic nanoparticles (or anisotropic nanostructures) orient in afirst direction, e.g., orthogonal to a plane of polarized light, suchthat substantially no light is transmitted, reflected or emitted in theabsence of a stimulus. In response to a stimulus, the anisotropicnanoparticles may change their orientation, e.g., to be parallel to theplane of polarized light, so that light may be transmitted, reflected oremitted. In other examples, the anisotropic nanoparticles (oranisotropic nanostructures) orient in a first direction, e.g., parallelto a plane polarized light, such that light is transmitted, reflected oremitted in the absence of a stimulus. In response to a stimulus, theanisotropic nanoparticles (or anisotropic nanostructures) may changetheir orientation, e.g., to be orthogonal to the plane of polarizedlight, so that substantially no light may be transmitted, reflected oremitted in the presence of the stimulus. In some examples, theanisotropic nanoparticles (or anisotropic nanostructures) are dispersedwith liquid crystals or disposed in a host matrix of the liquidcrystals, and as the liquid crystals alter their orientation in responseto a stimulus, the anisotropic nanoparticles (or anisotropicnanostructures) orient in the same manner as the liquid crystals. Asused herein in the context of a host matrix of the liquid crystals, theterm “dispose” refers to coating, impregnating, intercalating or addingnanoparticles or nanostructures to the host matrix. Additionalconfigurations will be readily selected by the person of ordinary skillin the art, given the benefit of this disclosure.

In accordance with certain examples, in an LC material containingplasmon supporting symmetrical or anisotropic nanoparticles, the plasmonabsorption and scattering may change in magnitude and wavelength whenthe surrounding material, e.g., LC, changes its optical properties inthe presence of a stimulus, e.g., an applied field. This result may beused alone or with the orientation effect to enhance or create contrastfor a pixel. In certain examples, elongated particles (e.g., nanotubes,nanorods, core shell structures and other high aspect ratio structures)of carbon, semiconductors, dielectrics, metals or composite structuresbased on these materials may also be used as a means of lowering ormodifying the switching and stability properties of liquid crystallinephases in the absence or presence of a stimulus, such as an electric,magnetic or acoustic field. The person of ordinary skill in the art,given the benefit of this disclosure, will be able to design suitablepixels using anisotropic nanoparticles and anisotropic nanostructures.

In accordance with certain examples, the exact configuration of thepixel may vary and, for illustrative purposes only, several exemplarypixel configurations are described herein. In certain examples, thepixel format may be based on the differential absorption and scatteringby anisotropic nanoparticles of metal or semiconductors or combinationsof both, including plasmonic and internal electron hole processes or acombination of both. In some examples the pixel may be activated toabsorb or scatter light differently by orienting the particles inresponse to a stimulus, such as, for example, an electric field or amagnetic field or both.

An example of this type of pixel is shown schematically in FIGS. 4A and4B. Though FIGS. 4A and 4B refer to anisotropic nanoparticles, it willbe recognized by the person of ordinary skill in the art, given thebenefit of this disclosure, that anisotropic nanostructures may be usedin place of, or in addition to, the anisotropic nanoparticles. Referringnow to FIG. 4A, an anisotropic nanoparticle in a first state 50 and aliquid crystal in a first state 60 may each be oriented substantiallyperpendicular (e.g., in the X-Y plane), in the absence of a stimulus, toa plane of incoming light (e.g., light polarized in the Z-direction)from, for example, backlight 69. Surfaces 65 and 66 may take the form ofelectrodes, for example, for application of an electric field. In thefirst state, the anisotropic particles and the liquid crystals mayprevent transmittance or reflectance of light or may allow transmittanceor reflectance of light depending on the plane of polarization of thelight. Referring now to FIG. 4B, as a stimulus, such as an electricfield, for example, is applied, the anisotropic particle may orient in asecond state 52 and the liquid crystal may orient in a second state 62,e.g., each may orient parallel to the Z-direction. In the second statethe anisotropic particles and the liquid crystals may preventtransmittance or reflectance of light or may allow transmittance orreflectance of light depending on the plane of polarization of thelight. In some examples, the pixel in the first state may transmit orreflect a first color, e.g., red, but in a second state, may transmit orreflect a different color, e.g., green or blue. The pixel may alsoinclude other optional features, such as polarizer 68. It will be withinthe ability of the person of ordinary skill in the art, given thebenefit of this disclosure, to design suitable transmissive orreflective pixels.

In accordance with certain examples, another pixel configuration may bebased on the differential absorption, transmission or scattering byanisotropic nanoparticles or anisotropic nanostructures, such as carbonnanotubes with or without associated nanoparticles and/or chromophores.Illustrative carbon nanotubes may be single wall, multiwall, associatedwith one or more chromophores so that the nanotube may provide thetorque and the chromophore may provide additional absorption or emissionbands. The person of ordinary skill in the art, given the benefit ofthis disclosure, will be able to design suitable pixels based on thedifferential absorption, transmission or scattering by anisotropicnanoparticles and/or anisotropic nanostructures.

In accordance with certain examples, the pixels disclosed herein may beilluminated from a top surface of the pixel or may be illuminated from abottom or back surface of the pixel. For example, if illuminated fromthe top surface, the pixel may be considered passive and may locallychange colors in a pixelated format. Similarly, if illuminated from theback surface, the effect may be used to affect the transmission ofvarious light sources to create the image. Suitable light sources forilluminating the pixels will be readily selected by the person ofordinary skill in the art, given the benefit of this disclosure, andexemplary light sources include, but are not limited to, lamps, e.g.,lamps emitting visible light, and light sources commonly used in liquidcrystal displays.

In accordance with certain examples, an additional example of a pixelmay be based on the orientation of concentrated anisotropicnanoparticles (or concentrated anisotropic nanostructures). Concentratedforms of anisotropic aggregates may take numerous forms including, forexample, fractal structures, linear forms, cross-shaped forms, T-shapedforms, trapezoid-shaped forms, U-shaped forms, gamma-shaped forms,corner-shaped forms or other suitable forms that the aggregate mayadopt. The exact composition of the nanostructure depends at least inpart on the intended use and in certain examples the nanostructure maybe a string of spherical particles on carbon nanotubes or sphericalparticles attached to a biopolymer, such as a polypeptide or apolynucleotide. Additional nanoparticle and/or nanostructureconfigurations suitable will be readily selected by the person ofordinary skill in the art, given the benefit of this disclosure.

In accordance with certain examples, an addition pixel configuration isshown schematically in FIGS. 5A and 5B. In the illustrativeconfiguration shown in FIGS. 5A and 5B, the pixel is configured for usein an emissive display, e.g., based on optical pumping (UV pumping forexample and different emission colors created by alloying, quantum sizeeffect and aspect ratios) of fluorescent particles of semiconductornanorods or carbon nanotubes with or without associated chromophores.These nanotubes may include associated chromophores, semiconductornanoparticles or quantum dots so that the nanotube may provide thetorque and the nanotube and or the chromophore, semiconductornanoparticles or quantum dots may provide the light emission. Referringto FIG. 5A, a pixel comprises an anisotropic nanostructure in a firststate 70, a liquid crystal in a first state 80 and surfaces 85 and 86,which may take the form of electrodes. The pixel may also include apolarizer 87 and a UV source 88, which can provide excitation light thatmay or may not be polarized, e.g., may be polarized in the X-Y plane asshown in FIGS. 5A and 5B. Because the nanostructure and liquid crystalare oriented in the X-Y plane in FIG. 5A, a strong fluorescence emission(or other luminescent emission depending on the chromophore) from thepixel may be observed. If the nanorods or carbon nanotube structures arerandomly oriented, they absorb an amount that is a function of thesingle particle absorption anisotropy and the macroscopic ensembleorientation. The emission may likewise be a function of their ensembleorientation and their absorption and emission anisotropy. Referring nowto FIG. 5B, as the nanostructure orients in a second state 72 and theliquid crystal orients in a second state 82 (e.g., each orient parallelto the Z-direction) in response to a stimulus, such as an electricfield, the fluorescence emission of the pixel may change from a strongfluorescence emission to a weak fluorescence emission. Alternatively,the fluorescence emission wavelength may be shifted, e.g., red-shiftedor blue-shifted, after orientation of the nanostructure and the liquidcrystal. Suitable UV sources include but are not limited to discharge orsolid state devices such as GaN LEDs or lasers, cathode ray lamps, arclamps and the like. It will be within the ability of the person ofordinary skill in the art, given the benefit of this disclosure, todesign suitable emission pixels using anisotropic nanoparticles andanisotropic nanostructures.

In accordance with certain examples, the anisotropic nanoparticles andanisotropic nanostructures may be dispersed with liquid crystalmaterials or be encapsulated to form microcapsules (see, e.g., FIG. 7).A pixel may include a single microcapsule or may include a plurality ofmicrocapsules. Each of the plurality of microcapsules in a pixel may bethe same or may be different. In addition, each microcapsule may includethe same anisotropic nanoparticles and anisotropic nanostructures or mayinclude different anisotropic nanoparticles and anisotropicnanostructures. The person of ordinary skill in the art, given thebenefit of this disclosure, will be able to design suitablemicrocapsules comprising anisotropic nanoparticles and anisotropicnanostructures.

In accordance with certain examples, the anisotropic nanoparticles andanisotropic nanostructures may be disposed or dispersed in voids of apolymer dispersed liquid crystal (PDLC) host as shown in FIG. 8. Forexample, microcapsule 100 comprises a PDLC host including a liquidcrystal material and one or more of an anisotropic nanoparticle and ananisotropic nanostructure disposed in the PDLC host. The exact nature ofthe polymer host can vary depending on the selected liquid crystals, butpreferably the polymer host does not substantially interfere, or reduce,the optical response and properties of the pixel or reduce the visualenhancement provided by the anisotropic nanoparticle and/or theanisotropic nanostructure. The polymer host may be chiral or achiral,may be colored or colorless or may take other suitable forms.Illustrative polymer hosts include, for example, NOA 73 and NOA 76, eachof which is commercially available from Norland Products (Cranbury,N.J.). Additional polymer hosts will be readily selected by the personof ordinary skill in the art, given the benefit of this disclosure.

In accordance with certain examples, the pixel may also includeadditional components and devices necessary to apply a stimulus, e.g.,an electric field or a magnetic field, to orient the materials in thepixel. For example, the pixel may include electrodes for applyingelectric fields and/or magnetic fields or for creating temperaturegradients, may include sound wave or pressure generators or may includeadditional devices configured to apply suitable stimuli to the LCs,nanoparticles, nanostructures or microcapsules in the pixel. One or moresurfaces of the pixel may also include a filter or material configuredto remove unwanted glares, ultraviolet light reflections, or ultravioletlight transmissions, from the light reflected or transmitted by thepixel. One or more surfaces may include polarizers or materialsconfigured to polarize the light. Additional components and devicesuseful with the pixels disclosed herein will be readily, selected by theperson of ordinary skill in the art, given the benefit of thisdisclosure.

In accordance with certain examples, a liquid crystal display comprisinga pixel as disclosed herein is provided. The liquid crystal display alsoincludes one or more liquid crystal materials. In certain examples, thedisplay may include a plurality of pixels as provided herein. Each ofthe pixels of the display may be constructed as described herein, or maybe constructed using additional suitable methods that will be readilyselected by the person of ordinary skill in the art, given the benefitof this disclosure. In certain examples, the display is configured as aflat panel display, e.g., a liquid crystal display. Each of the pixelsmay be configured to provide light that varies over a visible wavelengthrange, e.g., any wavelength between, and including 380-800 nm, or otherselected wavelength range, e.g., infrared or ultraviolet. It will bewithin the ability of the person of ordinary skill in the art, given thebenefit of this disclosure to design suitable liquid crystal displaysincluding the pixels disclosed herein.

In accordance with certain examples, the display may also includesuitable additional components and devices. For example, the display mayinclude a lamp or light source for illuminating the pixels. The displaymay also include suitable polarizers, such as those found in liquidcrystal displays. The display may include a power supply and suitableinterfaces for receiving signals, e.g., signals from a graphics card, atelevision tuner or the like. It will be within the ability of theperson of ordinary skill in the art, given the benefit of thisdisclosure, to design suitable displays using the pixels disclosedherein.

In accordance with certain examples, an ink comprising a liquid crystalmaterial and one or more of an anisotropic nanoparticle and ananisotropic nanostructure is provided. In certain examples, theanisotropic nanoparticle or the anisotropic nanostructure remains free,whereas in other examples, the anisotropic nanoparticle or theanisotropic nanostructure may be encapsulated, with or without the LCmaterial, to form microcapsules. In some examples, the anisotropicnanoparticle or the anisotropic nanostructure may be placed in a carrierprior to use as an ink. Referring to FIG. 7, anisotropic nanoparticlesor anisotropic nanostructures have been encapsulated to formmicrocapsules 90 and 92 which are disposed in a carrier 94. Suitablecarriers will be readily selected by the person of ordinary skill in theart, given the benefit of this disclosure and illustrative carriersinclude, but are not limited to, paste ink carrier (which may consist ofa small amount of solvent and/or phenolic resins, and/or alkyd resins,and/or nitrocellulose, and/or rosin maleic ester, and/or thinning oils,and/or waxes, and/or metal salt driers), UV curing type ink carriers, UVcuring type inks carrier that are variable in viscosity and are freeradical vehicles which may consist of about 5-80% acrylated oligomer(s)such a acrylated polyurethanes, acrylated polyesters, and acrylatedepoxies, 5-90% acrylated monomer(s) such as 1,6-hexanedioldiacrylate, oralkoxylated tetrahydrofurfuryl acrylate, or trimethylolpropanetrimethylacrylate, 0.1-10% photoinitiator(s) such as derivatives ofbenzophenone, phosphine oxides, 0-10% amine synergist and 0-20% adhesionpromoters such as multifunctional acid esters (all of which arecommercially available from Sartomer Company, Inc. (Exton, Pa.)).Examples of resin blends and dispersion vehicles that are suitable foruse as carriers include, for example, those commercially available fromLawter Intl., Inc. (Pleasant Prairie, Wis.). Additional carrierssuitable for use with anisotropic nanoparticles, anisotropicnanostructures and LC materials to provide inks will be readily selectedby the person of ordinary skill in the art, given the benefit of thisdisclosure. The microcapsules in the carrier may be disposed in a filledregion and their optical response controlled through the aggregation,proximity or by the concentration of the microcapsules to impart adesired color response.

In accordance with certain examples, the pixels, displays and inksdisclosed herein may be implemented in microencapsulated forms where theanisotropic nanoparticles and/or nanostructures, e.g., carbon based,semiconductor, metallic or a combination of these materials, are ineither a conventional or LC type fluid. Small capsules where surfaceenergy anchoring forces dominate may also be bistable. This feature mayallow for a zero or minimal power consumption mode in both states ofoperation. In the ideal case, a stimulus, e.g., a voltage, may beapplied that results in an orientation that remains in the absence ofthe stimulus due to surface anchoring forces or other energyconsiderations. FIG. 9 shows an example of a pixel having a bistablevoltage region. Additional configurations using bistable pixels,displays and inks will be readily selected by the person of ordinaryskill in the art, given the benefit of this disclosure.

In accordance with certain examples, a method of doping a pixel isprovided. In certain examples, the method includes doping a liquidcrystal display pixel with an anisotropic nanoparticle. In certainexamples, the method includes doping a liquid crystal display pixel withan anisotropic nanostructure. In certain examples, the liquid crystaldisplay pixel is doped with an effective amount of one or more of ananisotropic nanoparticle and an anisotropic nanostructure. The amount ofdopant used may be an amount effective to provide a desired visualenhancement of a pixel but is typically less than the amount that wouldalter the enhancement mechanism. In certain examples, the liquid crystaldisplay pixel is doped with an effective amount of an anisotropicnanoparticle or an anisotropic nanostructure to reduce chromaticdistortion as a function of viewing angle when non-orthogonal, e.g.,reduce chromatic distortion by at least about 10%. It will be within theability of the person of ordinary skill in the art, given the benefit ofthis disclosure, to design pixels and displays having reduced chromaticdistortion and wide viewing angles.

In accordance with certain examples, a method of facilitating visualenhancement of a pixel is disclosed. In certain examples, the methodincludes providing a pixel comprising a liquid crystal material and oneor more of an anisotropic nanoparticle or an anisotropic nanostructure.In some examples, the method includes encapsulating one or more of oneor more of a liquid crystal material, an anisotropic nanoparticle and ananisotropic nanostructure.

When introducing elements of the examples disclosed herein, the articles“a,” “an,” “the” and “said” are intended to mean that there are one ormore of the elements. The terms “comprising,” “including” and “having”are intended to be open ended and mean that there may be additionalelements other than the listed elements. It will be recognized by theperson of ordinary skill in the art, given the benefit of thisdisclosure, that various components of the examples can be interchangedor substituted with various components in other examples. Should themeaning of the terms of any of the patents, patent applications orpublications referred to herein conflict with the meaning of the termsused in this disclosure, the meaning of the terms in this disclosure areintended to be controlling.

Although certain aspects, examples and embodiments have been describedabove, it will be recognized by the person of ordinary skill in the art,given the benefit of this disclosure, that additions, substitutions,modifications, and alterations of the disclosed illustrative aspects,examples and embodiments are possible.

1. A pixel comprising a liquid crystal material and one or more of ananisotropic nanoparticle and an anisotropic nanostructure.
 2. The pixelof claim 1 in which the pixel is configured to reduce chromaticdistortion as a function of viewing angle when non-orthogonal.
 3. Thepixel of claim 2 in which the chromatic distortion is reduced by atleast about 10%.
 4. The pixel of claim 1 in which the anisotropicnanoparticle or the anisotropic nanostructure includes one or moremembers selected from the group consisting of silver, gold, platinum,palladium, ruthenium, rhodium, osmium, iridium, and alloys thereof. 5.The pixel of claim 1 further comprising two different anisotropicnanoparticles or two different anisotropic nanostructures.
 6. The pixelof claim 1 in which the liquid crystal material comprises one or moremembers selected from the group consisting of a nematic liquid crystal,a twisted nematic liquid crystal, a ferroelectric liquid crystal, asurface stabilized ferroelectric liquid crystal, and an E7 liquidcrystal.
 7. The pixel of claim 1 in which the anisotropic nanoparticleor the anisotropic nanostructure provides a differential absorption,transmission or scattering response.
 8. The pixel of claim 1 in whichthe anisotropic nanostructure comprises an anisotropic nanotube or ananisotropic nanorod.
 9. The pixel of claim 8 in which the anisotropicnanotube comprises one or more members selected from the groupconsisting of a single wall nanotube, a multiwall nanotube, a singlewall nanotube comprising an associated chromophore and a multiwallnanotube comprising an associated chromophore.
 10. The pixel of claim 1in which the anisotropic nanoparticle or the anisotropic nanostructureemits light in response to excitation.
 11. The pixel of claim 1 in whichthe anisotropic nanoparticle or the anisotropic nanostructure isdisposed in a liquid crystal host material.
 12. The pixel of claim 1 inwhich the anisotropic nanoparticle or the anisotropic nanostructure isencapsulated to form a microcapsule.
 13. The pixel of claim 12 in whichthe liquid crystal material is encapsulated in the microcapsule.
 14. Thepixel of claim 1 in which the anisotropic nanoparticle or theanisotropic nanostructure comprises a semiconductor.
 15. A liquidcrystal display comprising the pixel of claim
 1. 16. The liquid crystaldisplay of claim 15 in which each pixel of the liquid crystal displaycomprises the pixel of claim
 1. 17. An ink comprising a liquid crystalmaterial and one or more of an anisotropic nanoparticle and ananisotropic nanostructure.
 18. The ink of claim 17 in which theanisotropic nanoparticle or the anisotropic nanostructure isencapsulated to form a microcapsule.
 19. The ink of claim 17 in whichthe liquid crystal material is one or more members selected from thegroup consisting of a nematic liquid crystal, a twisted nematic liquidcrystal, a ferroelectric liquid crystal, a surface stabilizedferroelectric liquid crystal, and an E7 liquid crystal.
 20. The ink ofclaim 17 further comprising a carrier.
 21. The ink of claim 20 in whichthe carrier is a paste ink carrier, a UV curing type ink carrier, orcombinations thereof.
 22. A method comprising doping a liquid crystaldisplay pixel with one or more of an anisotropic nanoparticle and ananisotropic nanostructure.
 23. The method of claim 22 further comprisingconfiguring the anisotropic nanoparticle or the anisotropicnanostructure to be present in an amount effective to reduce chromaticdistortion, as a function of viewing angle when non-orthogonal, by atleast about 10%.
 24. A method of facilitating visual enhancement of apixel by providing a pixel comprising a liquid crystal material and oneor more of an anisotropic nanoparticle and an anisotropic nanostructure.